Derivatives of native lignin

ABSTRACT

The present invention provides derivatives of native lignin having a certain aliphatic hydroxyl content. Surprisingly, it has been found that consistent and predictable antioxidant activity may be provided by selecting for derivatives of native lignin having a certain aliphatic hydroxyl content.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application claims benefit of U.S. Provisional Patent ApplicationSer. No. 61/182,044, filed on May 28, 2009, and U.S. Provisional PatentApplication Ser. No. 61/233,345, filed Aug. 12, 2009, the contents ofwhich are incorporated in their entirety herein by reference.

FIELD

This invention relates to derivatives of native lignin recovered fromlignocellulosic feedstocks, and industrial applications thereof. Moreparticularly, this invention relates to derivatives of native ligninhaving certain chemical properties as well as uses, processes, methods,and compositions thereof.

BACKGROUND

Native lignin is a naturally occurring amorphous complex cross-linkedorganic macromolecule that comprises an integral component of all plantbiomass. The chemical structure of lignin is irregular in the sense thatdifferent structural units (e.g., phenylpropane units) are not linked toeach other in any systematic order. It is known that native lignincomprises pluralities of two monolignol monomers that are methoxylatedto various degrees (trans-coniferyl alcohol and trans-sinapyl alcohol)and a third non-methoxylated monolignol (trans-p-coumaryl alcohol).Various combinations of these monolignols comprise three building blocksof phenylpropanoid structures i.e. guaiacyl monolignol, syringylmonolignol and p-hydroxyphenyl monolignol, respectively, that arepolymerized via specific linkages to form the native ligninmacromolecule.

Extracting native lignin from lignocellulosic biomass during pulpinggenerally results in lignin fragmentation into numerous mixtures ofirregular components. Furthermore, the lignin fragments may react withany chemicals employed in the pulping process. Consequently, thegenerated lignin fractions can be referred to as lignin derivativesand/or technical lignins. As it is difficult to elucidate andcharacterize such complex mixture of molecules, lignin derivatives areusually described in terms of the lignocellulosic plant material used,and the methods by which they are generated and recovered fromlignocellulosic plant material, i.e. hardwood lignins, softwood lignins,and annual fibre lignins.

Native lignins are partially depolymerized during the pulping processesinto lignin fragments which dissolve in the pulping liquors andsubsequently separated from the cellulosic pulps. Post-pulping liquorscontaining lignin and polysaccharide fragments, and other extractives,are commonly referred to as “black liquors” or “spent liquors”,depending on the pulping process. Such liquors are generally considereda by-product, and it is common practice to combust them to recover someenergy value in addition to recovering the cooking chemicals. However,it is also possible to precipitate and/or recover lignin derivativesfrom these liquors. Each type of pulping process used to separatecellulosic pulps from other lignocellulosic components produces ligninderivatives that are very different in their physico-chemical,biochemical, and structural properties.

Given that lignin derivatives are available from renewable biomasssources there is an interest in using these derivatives in certainindustrial applications. For example, lignin derivatives obtained viaorganosols extraction, such as the Alcell® process (Alcell is aregistered trademark of Lignol Innovations Ltd., Burnaby, BC, CA), havebeen used in rubber products, adhesives, resins, plastics, asphalt,cement, casting resins, agricultural products, oil-field products and asfeedstocks for the production of fine chemicals. However, large-scalecommercial application of the extracted lignin derivatives, particularlythose isolated in traditional pulping processes employed in themanufacture of pulp for paper production, has been limited due to, forexample, the inconsistency of their chemical and functional properties.This inconsistency may, for example, be due to changes in feedstocksupplies and the particular extraction/generation/recovery conditions.These issues are further complicated by the complexity of the molecularstructures of lignin derivatives produced by the various extractionmethods and the difficulty in performing reliable routine analyses ofthe structural conformity and integrity of recovered lignin derivatives.For instance, lignin derivatives are known to have antioxidantproperties (e.g. Catignani G. L., Carter M. E., Antioxidant Propertiesof Lignin, Journal of Food Science, Volume 47, Issue 5, 1982, p. 1745;Pan X. et al. J. Agric. Food Chem., Vol. 54, No. 16, 2006, pp.5806-5813) but, to date, these properties have been highly variablemaking the industrial application of lignin derivatives as anantioxidant problematic.

Thermoplastics and thermosets are used extensively for a wide variety ofpurposes. Examples of thermoplastics include classes of polyesters,polycarbonates, polylactates, polyvinyls, polystyrenes, polyamides,polyacetates, polyacrylates, polypropylene, and the like. Polyolefinssuch as polyethylene and polypropylene represent a large market,amounting to more than 100 million metric tons annually. Duringmanufacturing, processing and use the physical and chemical propertiesof certain thermoplastics can be adversely affected by various factorssuch as exposure to heat, UV radiation, light, oxygen, mechanical stressor the presence of impurities. Clearly it is advantageous to mitigate oravoid these problems. In addition, the increase in recycling of materialhas led to an increased need to address these issues.

Degradation caused by free radicals, exposure to UV radiation, heat,light, and environmental pollutants are frequent causes of the adverseeffects. A stabilizer such as an antioxidant, anti-ozonant, or UV blockis often included in thermoplastic resins for the purpose of aiding inthe production process and extending the useful life of the product.Common examples of stabilizers and antioxidants include amine types,phenolic types, phenol alkanes, phosphites, and the like. Theseadditives often have undesirable or even unacceptable environmental,health and safety, economic, and/or disposal issues associated withtheir use. Furthermore, certain of these stabilizers/antioxidants canreduce the biodegradability of the product.

It has been suggested that lignin may provide a suitable polymericnatural antioxidant which has an acceptable toxicity, efficacy, andenvironmental profile. See, for example, A. Gregorova et al., Radicalscavenging capacity of lignin and its effect on processing stabilizationof virgin and recycled polypropylene, Journal of Applied Polymer Science106-3 (2007) pp. 1626-1631; C. Pouteau et al. Antioxidant Properties ofLignin in Polypropylene, Polymer Degradation and Stability 81 (2003)9-18. Despite the advantages of lignin, for a variety of reasons, it hasnot been adopted for widespread use as an antioxidant. For instance, itis often problematic to provide lignins that perform consistently interms of antioxidant activity. Also, the processing of the lignin mayintroduce substances that are incompatible for use with chemicals suchas polyolefins. Additionally, the cost of producing and/or purifying thelignin may make it uneconomic for certain uses.

SUMMARY

The present invention provides derivatives of native lignin having acertain aliphatic hydroxyl content. Surprisingly, it has been found thatconsistent and predictable antioxidant activity may be provided byselecting for derivatives of native lignin having certain aliphatichydroxyl contents.

As used herein, the term “native lignin” refers to lignin in its naturalstate, in plant material.

As used herein, the terms “lignin derivatives” and “derivatives ofnative lignin” refer to lignin material extracted from lignocellulosicbiomass. Usually, such material will be a mixture of chemical compoundsthat are generated during the extraction process.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the HSQC spectrum of non-acetylated hardwood ligninderivatives (arrows indicate the signals corresponding to the ethoxylgroups).

FIG. 2 shows the quantitative ¹³C NMR spectrum of non-acetylatedhardwood lignin derivatives.

FIG. 3 shows the quantitative ¹³C NMR spectrum of acetylated hardwoodlignin derivatives.

DETAILED DESCRIPTION

The present invention provides derivatives of native lignin havingcertain aliphatic hydroxyl contents. Lignin derivatives having loweraliphatic hydroxyl contents have been found to score more highly on theRadical Scavenging Index (RSI), a measure of antioxidant activity. Thus,selecting for derivatives of native lignin having a lower aliphatichydroxyl content results in a product having a higher and morepredictable antioxidant activity. It has been found that derivatives ofnative lignin having an aliphatic hydroxyl content of about 2.35 mmol/gor less result in a good level of antioxidant activity. For example,about 2.25 mmol/g or less, about 2 mmol/g or less, or about 1.75 mmol/gor less.

Radical Scavenging Index (RSI) is a measure of radical scavengingcapacity. The assay uses 2,2-diphenyl-1-picrylhydrazyl (DPPH), a stablefree radical which absorbs light strongly at 515 nm, to measure acompound's radical scavenging index (RSI). In its radical form, DPPH•absorbs strongly at 515 nm and has a deep purple colour. As DPPH givesup its free electron to radical scavengers, it loses its purple colourand its absorbance shifts to 520 nm. The greater the drop in DPPHabsorbance at 515 nm after a test compound has been added to the DPPHsolution, the higher the compound's free RSI and also, its antioxidantactivity. In the present invention, Vitamin E (Vit. E) and butylatedhydroxytoluene (BHT) are used as positive controls. The ligninderivative samples (1.0-2.0 mg), Vit. E control samples (1.0-2.0 mg),and BHT control samples (6.0-8.0 mg) are prepared for testing by beingplaced into microcentrifuge tubes after which each was diluted with 1.0mL of 90% (v/v) aqueous dioxan, vortexed, transferred to newmicrocentrifuge tubes and further diluted 50/50 with 90% aqueous dioxaneto give stock concentrations of 0.5-1.0 mg/mL for samples and Vitamin Eand 3.0-4.0 mg/mL for BHT. An indicating (purple) DPPH stable freeradical solution is made by dissolving 3.78 mg DPPH in 100 mL 90%dioxane (95.9 μM). Samples and standards are serially diluted to fillcolumns of a quartz 96-well plate (8 dilutions). The assays areperformed by placing aliquots of the sample stock solutions into tworows of wells in a 96-well plate. The first row served as the referencerow while the second row received DPPH aliquots. 165 μL, of 90% dioxanewas added to each well and mixed. Aliquots of the mixed samples in eachrow are transferred to the adjacent row which is further diluted with165 μL, of 90% dioxane in each well. The mixing, transferring anddilution are repeated until the last row of wells is prepared. The samevolume of aliquots is removed from the last row. The 96-well plate alsocontains a row of wells that received only the 90% dioxane. In the finalstep of the preparation procedure, 165 μL of the DPPH solution is addedas quickly as possible to all the control and analytical columns byusing an 8-channel auto-pipette and an Eppendorf® reagent reservoir. Assoon as all reagents are added, the plate is placed into a plate-readingspectrophotometer (Spectra Max Plus, Molecular Devices, Sunnyvale,Calif., USA), and absorbance measurements are carried out. The programfor the spectrophotometer (SOFTmax software) consists of a timingsequence of 16 min and a reading of the entire plate at 515 nm. RSI isdefined as the inverse of the concentration which produces 50%inhibition in DPPH absorbance at 515 nm. The results are then‘normalized’ by dividing the sample RSI by the RSI value for the BHTcontrol. The normalized RSI is represented by this acronym “NRSI”.

The present invention provides derivatives of native lignin recoveredduring or after pulping of lignocellulosic feedstocks. The pulp may befrom any suitable lignocellulosic feedstock including hardwoods,softwoods, annual fibres, and combinations thereof.

Hardwood feedstocks include Acacia; Afzelia; Synsepalum duloificum;Albizia; Alder (e.g. Alnus glutinosa, Alnus rubra); Applewood; Arbutus;Ash (e.g. F. nigra, F. quadrangulata, F. excelsior, F. pennsylvanicalanceolata, F. latifolia, F. profunda, F. americana); Aspen (e.g. P.grandidentata, P. tremula, P. tremuloides); Australian Red Cedar (Toonaciliata); Ayna (Distemonanthus benthamianus); Balsa (Ochromapyramidale); Basswood (e.g. T americana, T. heterophylla); Beech (e.g.F. sylvatica, F. grandifolia); Birch; (e.g. Betula populifolia, B.nigra, B. papyrifera, B. lenta, B. alleghaniensis/B. lutea, B. pendula,B. pubescens); Blackbean; Blackwood; Bocote; Boxelder; Boxwood;Brazilwood; Bubing a; Buckeye (e.g. Aesculus hippocastanum, Aesculusglabra, Aesculus flava/Aesculus octandra); Butternut; Catalpa; Cherry(e.g. Prunus serotina, Prunus pennsylvanica, Prunus avium); Crabwood;Chestnut; Coachwood; Cocobolo; Corkwood; Cottonwood (e.g. Populusbalsamifera, Populus deltoides, Populus sargentii, Populusheterophylla); Cucumbertree; Dogwood (e.g. Cornus florida, Cornusnuttallii); Ebony (e.g. Diospyros kurzii, Diospyros melanida, Diospyroscrassiflora); Elm (e.g. Ulmus americana, Ulmus procera, Ulmus thomasii,Ulmus rubra, Ulmus glabra); Eucalyptus; Greenheart; Grenadilla; Gum(e.g. Nyssa sylvatica, Eucalyptus globulus, Liquidambar styraciflua,Nyssa aquatica); Hickory (e.g. Carya alba, Carya glabra, Carya ovata,Carya laciniosa); Hornbeam; Hophornbeam; Ipê; Iroko; Ironwood (e.g.Bangkirai, Carpinus caroliniana, Casuarina equisetifolia,Choricbangarpia subargentea, Copaifera spp., Eusideroxylon zwageri,Guajacum officinale, Guajacum sanctum, Hopea odorata, Ipe,Krugiodendronferreum, Lyonothamnus lyonii (L. floribundus), Mesuaferrea, Olea spp., Olneya tesota, Ostrya virginiana, Parrotia persica,Tabebuia serratifolia); Jacarandá; Jotoba; Lacewood; Laurel; Limba;Lignum vitae; Locust (e.g. Robinia pseudacacia, Gleditsia triacanthos);Mahogany; Maple (e.g. Acer saccharum, Acer nigrum, Acer negundo, Acerrubrum, Acer saccharinum, Acer pseudoplatanus); Meranti; Mpingo; Oak(e.g. Quercus macrocarpa, Quercus alba, Quercus stellata, Quercusbicolor, Quercus virginiana, Quercus michauxii, Quercus prinus, Quercusmuhlenbergii, Quercus chrysolepis, Quercus lyrata, Quercus robur,Quercus petraea, Quercus rubra, Quercus velutina, Quercus laurifolia,Quercus falcata, Quercus nigra, Quercus phellos, Quercus texana);Obeche; Okoumé; Oregon Myrtle; California Bay Laurel; Pear; Poplar (e.g.P. balsamifera, P. nigra, Hybrid Poplar (Populus×canadensis)); Ramin;Red cedar; Rosewood; Sal; Sandalwood; Sassafras; Satinwood; Silky Oak;Silver Wattle; Snakewood; Sourwood; Spanish cedar; American sycamore;Teak; Walnut (e.g. Juglans nigra, Juglans regia); Willow (e.g. Salixnigra, Salix alba); Yellow poplar (Liriodendron tulipifera); Bamboo;Palmwood; and combinations/hybrids thereof.

For example, hardwood feedstocks for the present invention may beselected from Acacia, Aspen, Beech, Eucalyptus, Maple, Birch, Gum, Oak,Poplar, and combinations/hybrids thereof. The hardwood feedstocks forthe present invention may be selected from Populus spp. (e.g. Populustremuloides), Eucalyptus spp. (e.g. Eucalyptus globulus), Acacia spp.(e.g. Acacia dealbata), and combinations/hybrids thereof.

It has been found that derivatives of native lignin from hardwoodfeedstocks having an aliphatic hydroxyl content of about 2.35 mmol/g orless have a good level of antioxidant activity. For example, about 2.25mmol/g or less, about 2 mmol/g or less, or about 1.75 mmol/g or less.

In the present invention, “aliphatic hydroxyl content” refers to thequantity of aliphatic hydroxyl groups in the lignin derivatives and isthe arithmetic sum of the quantity of primary and secondary hydroxylgroups (OHal=OHpr+OHsec). The aliphatic hydroxyl content can be measuredby quantitative ¹³C high resolution NMR spectroscopy of acetylated andnon-acetylated lignin derivatives, using, for instance, 1,3,5-trioxaneand tetramethyl silane (TMS) as internal reference. For the dataanalysis “BASEOPT” (DIGMOD set to baseopt) routine in the softwarepackage TopSpin 2.1.4 was used to predict the first FID data point backat the mid-point of ¹³C r.f. pulse in the digitally filtered data wasused. For the NMR spectra recording a Bruker AVANCE II digital NMRspectrometer running TopSpin 2.1 was used. The spectrometer used aBruker 54 mm bore Ultrashield magnet operating at 14.1 Tesla (600.13 MHzfor ¹H, 150.90 MHz for ¹³C). The spectrometer was coupled with a BrukerQNP cryoprobe (5 mm NMR samples, ¹³C direct observe on inner coil, ¹Houter coil) that had both coils cooled by helium gas to 20K and allpreamplifiers cooled to 77K for maximum sensitivity. Sample temperaturewas maintained at 300 K±0.1 K using a Bruker BVT 3000 temperature unitand a Bruker BCU05 cooler with ca. 95% nitrogen gas flowing over thesample tube at a rate of 800 L/h.

The lignin derivatives herein may, for example, have an aliphatichydroxyl content of 0.001 mmol/g or greater; 0.1 mmol/g or greater; 0.2mmol/g or greater; 0.4 mmol/g or greater; 0.5 mmol/g or greater.

Quantification of ethoxyl groups was performed similarly to aliphatichydroxyls quantification by high resolution ¹³C NMR spectroscopy.Identification of ethoxyl groups was confirmed by 2D NMR HSQCspectroscopy. 2D NMR spectra were recorded by a Bruker 700 MHzUltraShield Plus standard bore magnet spectrometer equipped with asensitive cryogenically cooled 5 mm TCI gradient probe with inversegeometry. The acquisition parameters were as follow: standard Brukerpulse program hsqcetgp, temperature of 298 K, a 90° pulse, 1.1 sec pulsedelay (d1), and acquisition time of 60 msec.

Derivatives of native lignin according to the present invention, comingfrom hardwood feedstocks tend to have a NRSI of 30 or greater, 40 orgreater, 50 or greater, 60 or greater, 70 or greater, 80 or greater, 90or greater, 100 or greater, 110 or greater, 120 or greater.

Softwood feedstocks include Araucaria (e.g. A. cunninghamii, A.angustifolia, A. araucana); softwood Cedar (e.g. Juniperus virginiana,Thuja plicata, Thuja occidentalis, Chamaecyparis thyoides Callitropsisnootkatensis); Cypress (e.g. Chamaecyparis, Cupressus Taxodium,Cupressus arizonica, Taxodium distichum, Chamaecyparis obtusa,Chamaecyparis lawsoniana, Cupressus semperviren); Rocky Mountain Douglasfir; European Yew; Fir (e.g. Abies balsamea, Abies alba, Abies procera,Abies amabilis); Hemlock (e.g. Tsuga canadensis, Tsuga mertensiana,Tsuga heterophylla); Kauri; Kaya; Larch (e.g. Larix decidua, Larixkaempferi, Larix laricina, Larix occidentalis); Pine (e.g. Pinus nigra,Pinus banksiana, Pinus contorta, Pinus radiata, Pinus ponderosa, Pinusresinosa, Pinus sylvestris, Pinus strobus, Pinus monticola, Pinuslambertiana, Pinus taeda, Pinus palustris, Pinus rigida, Pinusechinata); Redwood; Rimu; Spruce (e.g. Picea abies, Picea mariana, Picearubens, Picea sitchensis, Picea glauca); Sugi; and combinations/hybridsthereof.

For example, softwood feedstocks which may be used herein include cedar;fir; pine; spruce; and combinations thereof. The softwood feedstocks forthe present invention may be selected from loblolly pine (Pinus taeda),radiata pine, jack pine, spruce (e.g., white, interior, black), Douglasfir, Pinus silvestris, Picea abies, and combinations/hybrids thereof.The softwood feedstocks for the present invention may be selected frompine (e.g. Pinus radiata, Pinus taeda); spruce; and combinations/hybridsthereof.

It has been found that derivatives of native lignin from softwoodfeedstocks having an aliphatic hydroxyl content of about 2.35 mmol/g orless have a good level of antioxidant activity. For example, about 2.25mmol/g or less, about 2 mmol/g or less, or about 1.75 mmol/g or less.

Derivatives of native lignin according to the present invention, comingfrom softwood feedstocks tend to have a NRSI 15 or greater, 25 orgreater, 30 or greater, 35 or greater, 40 or greater, 45 or greater, 50or greater, 55 or greater, 60 or greater.

Annual fibre feedstocks include biomass derived from annual plants,plants which complete their growth in one growing season and thereforemust be planted yearly. Examples of annual fibres include: flax, cerealstraw (wheat, barley, oats), sugarcane bagasse, rice straw, corn stover,corn cobs, hemp, fruit pulp, alfa grass, switchgrass, andcombinations/hybrids thereof. Industrial residues like corn cobs, fruitpeals, seeds, etc. may also be considered annual fibres since they arecommonly derived from annual fibre biomass such as edible crops andfruits. For example, the annual fibre feedstock may be selected fromwheat straw, corn stover, corn cobs, sugar cane bagasse, andcombinations/hybrids thereof.

Derivatives of native lignin according to the present invention, comingfrom annual fibre feedstocks tend to have a NRSI of 15 or greater, 20 orgreater, 25 or greater, 30 or greater, 35 or greater, 40 or greater, 45or greater, 50 or greater.

In an embodiment of the present invention, derivatives of native ligninfrom annual fibre feedstocks have an aliphatic hydroxyl content of about3.75 mmol/g or less; 3.5 mmol/g or less; 3.25 mmol/g or less; 3 mmol/gor less; 2.75 mmol/g or less; 2.5 mmol/g or less; 2.35 mmol/g or less;2.25 mmol/g or less.

The derivatives of native lignin will vary with the type of process usedto separate native lignins from cellulose and other biomassconstituents. Preparations very similar to native lignin can be obtainedby (1) solvent extraction of finely ground wood (milled-wood lignin,MWL) or by (2) acidic dioxane extraction (acidolysis) of wood.Derivatives of native lignin can be also isolated from biomasspre-treated using (3) steam explosion, (4) dilute acid hydrolysis, (5)ammonia fibre expansion, (6) autohydrolysis methods. Derivatives ofnative lignin can be recovered after pulping of lignocellulosicsincluding industrially operated (3) kraft and (4) soda pulping (andtheir modifications) and (5) sulphite pulping. In addition, a number ofvarious pulping methods have been developed but not industriallyintroduced. Among them four major “organosolv” pulping methods tend toproduce highly-purified lignin mixtures. The first organosolv methoduses ethanol/solvent pulping (aka the Alcell® process); the secondorganosolv method uses alkaline sulphite anthraquinone methanol pulping(aka the “ASAM” process); the third organosolv process uses methanolpulping followed by methanol, NaOH, and anthraquinone pulping (aka the“Organocell” process); the fourth organosolv process uses aceticacid/hydrochloric acid or formic acid pulping (aka the “Acetosolv”process).

It should be noted that kraft pulping, sulphite pulping, and ASAMorganosolv pulping will generate derivatives of native lignin containingsignificant amounts of organically-bound sulphur which may make themunsuitable for certain uses. Acid hydrolysis, soda pulping, steamexplosion, Alcell® pulping, Organocell pulping, and Acetosolv pulpingwill generate derivatives of native lignin that are sulphur-free orcontain low amounts of inorganic sulphur.

Organosolv processes, particularly the Alcell® process, tend to be lessaggressive and can be used to separate highly purified ligninderivatives and other useful materials from biomass without excessivelyaltering or damaging the native lignin building blocks. Such processescan therefore be used to maximize the value from all the componentsmaking up the biomass. Organosolv extraction processes however typicallyinvolve extraction at higher temperatures and pressures with a flammablesolvent compared to other industrial processes and thus are generallyconsidered to be more complex and expensive.

A description of the Alcell® process can be found in U.S. Pat. No.4,764,596 (herein incorporated by reference). The process generallycomprises pulping or pre-treating a fibrous biomass feedstock withprimarily an ethanol/water solvent solution under conditions thatinclude: (a) 60% ethanol/40% water, (b) temperature of about 180° C. toabout 210° C., (c) pressure of about 20 atm to about 35 atm, and (d) aprocessing time of 5-120 minutes. Derivatives of native lignin arefractionated from the native lignins into the pulping liquor which alsoreceives solubilised hemicelluloses, other carbohydrates and otherextractives such as resins, organic acids, phenols, and tannins.Organosolv pulping liquors comprising the fractionated derivatives ofnative lignin and other extractives from the fibrous biomass feedstocks,are often called “black liquors”. The organic acid and extractivesreleased by organosolv pulping significantly acidify the black liquorsto pH levels of about 5 and lower. After separation from the cellulosicpulps produced during the pulping process, the derivatives of nativelignin are recovered from the black liquors by depressurization followedby flashing with cold water which will cause the fractionatedderivatives of native lignin to precipitate thereby enabling theirrecovery by standard solids/liquids separation processes. Variousdisclosures exemplified by U.S. Pat. No. 7,465,791 and PCT PatentApplication Publication No. WO 2007/129921, describe modifications tothe Alcell organosolv process for the purposes of increasing the yieldsof fractionated derivatives of native lignin recovered from fibrousbiomass feedstocks during biorefining. Modifications to the Alcellorganosolv process conditions included adjusting: (a) ethanolconcentration in the pulping liquor to a value selected from a range of35%-85% (w/w) ethanol, (b) temperature to a value selected from a rangeof 100° C. to 350° C., (c) pressure to a value selected from a range of5 atm to 35 atm, and (d) processing time to a duration from a range of20 minutes to about 2 hours or longer, (e) liquor-to-wood ratio of 3:1to 15:1 or higher, (f) pH of the cooking liquor from a range of 1 to 6.5or higher if a basic catalyst is used.

The present invention provides a process for producing derivatives ofnative lignin, said process comprising:

(a) pulping a fibrous biomass feedstock with an organic solvent/watersolution,

(b) separating the cellulosic pulps or pre-treated substrates from thepulping liquor or pre-treatment solution,

(c) recovering derivatives of native lignin.

The organic solvent may be selected from short chain primary andsecondary alcohols, such as such as methanol, ethanol, propanol, andcombinations thereof. For example, the solvent may be ethanol. Theliquor solution may comprise about 20%, by weight, or greater, about 30%or greater, about 50% or greater, about 60% or greater, about 70% orgreater, of ethanol.

Step (a) of the process may be carried out at a temperature of fromabout 100° C. and greater, or about 120° C. and greater, or about 140°C. and greater, or about 160° C. and greater, or about 170° C. andgreater, or about 180° C. and greater. The process may be carried out ata temperature of from about 300° C. and less, or about 280° C. and less,or about 260° C. and less, or about 240° C. and less, or about 220° C.and less, or about 210° C. and less, or about 205° C. and less, or about200° C. and less.

Step (a) of the process may be carried out at a pressure of about 5 atmand greater, or about 10 atm and greater, or about 15 atm and greater,or about 20 atm and greater, or about 25 atm and greater, or about 30atm and greater. The process may be carried out at a pressure of about150 atm and less, or about 125 atm and less, or about 115 atm and less,or about 100 atm and less, or about 90 atm and less, or about 80 atm andless.

The fibrous biomass may be treated with the solvent solution of step (a)for about 1 minute or more, about 5 minutes or more, about 10 minutes ormore, about 15 minutes or more, about 30 minutes or more. The fibrousbiomass may be treated with the solvent solution of step (a) at itsoperating temperature for about 360 minutes or less, about 300 minutesor less, about 240 minutes or less, about 180 minutes or less, about 120minutes or less.

The pH of the pulp liquor may, for example, be from about 1 to about 6,or from about 1.5 to about 5.5.

The weight ratio of liquor to biomass may be any suitable ratio. Forexample, from about 5:1 to about 15:1, from about 5.5:1 to about 10:1;from about 6:1 to about 8:1.

The volume of extraction solution is from about 5 to about 10 times thevolume of the biomass feedstock. For example, the volume of extractionsolution may be from about 6 to about 8 times that of the biomass

The present invention provides a process for producing a ligninderivative having an aliphatic hydroxyl content of about 2.35 mmol/g orless, about 2.25 mmol/g or less, about 2 mmol/g or less, or about 1.75mmol/g or less. Said process comprises:

-   -   a) pulping or pre-treating a fibrous biomass feedstock in a        vessel with an organic solvent/water solution to form a liquor,        wherein:        -   i. the solution comprises about 30% or greater, by weight,            of organic solvent; and        -   ii. the pH of the liquor is from about 1 to about 6;    -   b) heating the liquor to about 100° C. or greater;    -   c) raising the pressure in the vessel to about 5 atm or greater;    -   d) maintaining the elevated temperature and pressure for 1        minute or longer;    -   e) separating the cellulosic pulps from the pulp liquor    -   f) recovering derivatives of native lignin.

The present invention provides a process for producing a hardwood ligninderivative having an aliphatic hydroxyl content of about 2.35 mmol/g orless, about 2.25 mmol/g or less, about 2 mmol/g or less, or about 1.75mmol/g or less, said process comprises:

-   -   a) pulping or pre-treating a fibrous biomass feedstock in a        vessel with an organic solvent/water solvent solution to form a        liquor, wherein:        -   i. the solution comprises about 30% or greater, by weight,            of organic solvent; and        -   ii. the pH of the liquor is from about 1 to about 6;    -   b) heating the liquor to about 100° C. or greater;    -   c) raising the pressure in the vessel to about 5 atm or greater;    -   d) maintaining the elevated temperature and pressure for 1        minute or longer;    -   e) separating the cellulosic pulps from the pulp liquor    -   f) recovering derivatives of native lignin.

The present invention provides a process for producing a softwood ligninderivative having an aliphatic hydroxyl content of about 2.35 mmol/g orless, about 2.25 mmol/g or less, about 2 mmol/g or less, or about 1.75mmol/g or less, said process comprises:

-   -   a) pulping or pre-treating a fibrous biomass feedstock in a        vessel with an organic solvent/water solvent solution to form a        liquor, wherein:        -   i. the solution comprises about 30% or greater, by weight,            of organic solvent; and        -   ii. the pH of the liquor is from about 1 to about 6;    -   b) heating the liquor to about 100° C. or greater;    -   c) raising the pressure in the vessel to about 5 atm or greater;    -   d) maintaining the elevated temperature and pressure for 1        minute or longer;    -   e) separating the cellulosic pulps from the pulp liquor    -   f) recovering derivatives of native lignin.

The present invention provides a process for producing an annual fibrelignin derivative having an aliphatic hydroxyl content of about 3.75mmol/g or less; 3.5 mmol/g or less; 3.25 mmol/g or less; 3 mmol/g orless; 2.75 mmol/g or less; 2.5 mmol/g or less; 2.35 mmol/g or less; 2.25mmol/g or less, said process comprises:

-   -   a) pulping or pre-treating a fibrous biomass feedstock in a        vessel with an organic solvent/water solvent solution to form a        liquor, wherein:        -   i. the solution comprises about 30% or greater, by weight,            of organic solvent; and        -   ii. the pH of the liquor is from about 1 to about 6;    -   b) heating the liquor to about 100° C. or greater;    -   c) raising the pressure in the vessel to about 5 atm or greater;    -   d) maintaining the elevated temperature and pressure for 1        minute or longer;    -   e) separating the cellulosic pulps from the pulp liquor    -   f) recovering derivatives of native lignin.

The derivatives of native lignin herein may be incorporated into polymercompositions. The compositions herein may comprise a lignin derivativeaccording to the present invention and a polymer-forming component. Asused herein, the term ‘polymer-forming component’ means a component thatis capable of being polymerized into a polymer as well as a polymer thathas already been formed. For example, in certain embodiments thepolymer-forming component may comprise monomer units which are capableof being polymerized. In certain embodiments the polymer component maycomprise oligomer units that are capable of being polymerized. Incertain embodiments the polymer component may comprise a polymer that isalready substantially polymerized.

Polymers forming components for use herein may result in thermoplasticor thermoset polymers such as epoxy resins, urea-formaldehyde resins,phenol-formaldehyde resins, polyimides, isocyanate resins, and the like.For example, polyalkenes such as polyethylene or polypropylene.

Typically, the lignin derivative will comprise from about 0.1%, byweight, or greater, about 0.5% or greater, about 1% or greater, of thecomposition. Typically, the lignin derivative will comprise from about80%, by weight, or less, about 60% or less, about 40% or less, about 20%or less, about 10% or less, of the composition.

The compositions comprise lignin derivative and polymer-formingcomponent but may comprise a variety of other optional ingredients suchas adhesion promoters; biocides (antibacterials, fungicides, andmoldicides), anti-fogging agents; anti-static agents; bonding, blowingand foaming agents; dispersants; fillers and extenders; fire and flameretardants and smoke suppressants; impact modifiers; initiators;lubricants; micas; pigments, colorants and dyes; plasticizers;processing aids; release agents; silanes, titanates and zirconates; slipand anti-blocking agents; stabilizers; stearates; ultraviolet lightabsorbers; foaming agents; defoamers; hardeners; odorants; deodorants;antifouling agents; viscosity regulators; waxes; and combinationsthereof.

The present invention provides the use of the present derivatives ofnative lignin as an antioxidant. For example, the present use may be asan antioxidant additive for use with thermoplastic polymers such aspolyethylene, polypropylene, polyamides, styrene-butadiene, naturalrubber, and combinations thereof. Other examples include: antioxidantadditives for use in the animal health and feed industry, human food andhealth.

The present invention provides methods of producing derivatives ofnative lignin having an aliphatic hydroxyl content of about 2.35 mmol/gor less, about 2.25 mmol/g or less, about 2 mmol/g or less, or about1.75 mmol/g or less.

The present invention provides methods of producing hardwood derivativesof native lignin having an aliphatic hydroxyl content of about 2.35mmol/g or less result, about 2.25 mmol/g or less, about 2 mmol/g orless, or about 1.75 mmol/g or less.

The present invention provides methods of producing softwood derivativesof native lignin having an aliphatic hydroxyl content of about 2.35mmol/g or less, about 2.25 mmol/g or less, about 2 mmol/g or less, orabout 1.75 mmol/g or less.

The present invention provides methods of producing annual fibrederivatives of native lignin having an aliphatic hydroxyl content ofabout 3.75 mmol/g or less; 3.5 mmol/g or less.

3.25 mmol/g or less; 3 mmol/g or less; 2.75 mmol/g or less; 2.5 mmol/gor less; 2.35 mmol/g or less; 2.25 mmol/g or less.

The present invention provides methods of producing derivatives ofnative lignin having a NRSI of 15 or greater, 20 or greater, 25 orgreater, 30 or greater, 35 or greater, 40 or greater, 50 or greater, 60or greater, 70 or greater.

The present invention provides methods of producing hardwood derivativesof native lignin having a NRSI of 15 or greater, 20 or greater, 25 orgreater, 30 or greater, 35 or greater, 40 or greater, 50 or greater, 60or greater, 70 or greater.

The present invention provides methods of producing softwood derivativesof native lignin having a NRSI of 15 or greater, 20 or greater, 25 orgreater, 30 or greater, 35 or greater, 40 or greater.

The present invention provides methods of producing annual fibrederivatives of native lignin having a NRSI of 15 or greater, 20 orgreater, 25 or greater, 30 or greater, 35 or greater.

The present invention provides lignin derivatives comprising alkoxygroups. For example, the present lignin derivatives may have an alkoxycontent of 2 mmol/g or less; about 1.4 mmol/g or less; about 1.2 mmol/gor less; about 1 mmol/g or less; about 0.8 mmol/g or less; about 0.7mmol/g or less; about 0.6 mmol/g or less; about 0.5 mmol/g or less;about 0.4 mmol/g or less; about 0.3 mmol/g or less. The present ligninderivatives may have an alkoxy content of 0.001 mmol/g or greater, about0.01 mmol/g of greater, about 0.05 mmol/g or greater, about 0.1 mmol/gor greater.

The present invention provides lignin derivatives comprising ethoxylgroups. For example, the present lignin derivatives may have an ethoxylcontent of 2 mmol/g or less; about 1.4 mmol/g or less; about 1.2 mmol/gor less; about 1 mmol/g or less; about 0.8 mmol/g or less; about 0.7mmol/g or less; about 0.6 mmol/g or less; about 0.5 mmol/g or less;about 0.4 mmol/g or less; about 0.3 mmol/g or less. The present ligninderivatives may have an ethoxyl content of 0.001 mmol/g or greater,about 0.01 mmol/g of greater, about 0.05 mmol/g or greater, about 0.1mmol/g or greater.

The present lignin derivatives may have any suitable phenolic hydroxylcontent such as from about 2 mmol/g to about 8 mmol/g. For example, thephenolic hydroxyl content may be from about 2.5 mmol/g to about 7mmol/g; about 3 mmol/g to about 6 mmol/g.

The present lignin derivatives may have any suitable number averagemolecular weight (Mn). For example, the Mn may be from about 200 g/molto about 3000 g/mol; about 350 g/mol to about 2000 g/mol; about 500g/mol to about 1500 g/mol.

The present lignin derivatives may have any suitable weight averagemolecular weight (Mw). For example, the Mw may be from about 500 g/molto about 5000 g/mol; about 750 g/mol to about 4000 g/mol; about 900g/mol to about 3500 g/mol.

The present lignin derivatives may have any suitable polydispersity (D).For example, the D may be from about 1 to about 5; from about 1.2 toabout 4; from about 1.3 to about 3.5; from about 1.4 to about 3.

The present lignin derivatives are preferably hydrophobic.Hydrophobicity may be assessed using contact angle measurements.

It has been suggested that lignins or lignin derivatives may be used innutritional supplements (e.g. Baurhoo et. al., Purified Lignin:Nutritional and Health Impacts on Farm Animals—A Review, Animal FeedScience and Technology 144 (2008) 175-184). The present derivatives ofnative lignin may be used in nutritional supplements, nutraceuticals,functional foods, and the like. The stable and consistent antioxidantactivity may be advantageous when formulating such compositions.

The present derivatives of native lignin may be used for other purposessuch as, for example, laminates, stains, pigments, inks, adhesives,coatings, rubbers, elastomers, plastics, films, paints, carbon fibrecomposites, panel boards, print-circuit boards, lubricants, surfactants,oils, animal feed, food and beverages, and the like.

EXAMPLES Example 1 Recovery of Lignin Derivatives from HardwoodFeedstocks

Hardwood feedstock chips were prepared from: (1) aspen (P. tremuloides)grown in British Columbia, Canada; (2) acacia (A. dealbata) grown inChile; and (3) eucalyptus (E. nitens) grown in Chile. Five samples ofthe aspen chips were individually pulped using an acid-catalyzed ethanolorganosolv pulping process wherein a different set of pulping conditionswas used for each sample (Table 1). Process conditions for pulping foursamples of the acacia chips are shown in Table 2. Process conditions forpulping four samples of the eucalyptus chips are shown in Table 3.

TABLE 1 Pulping conditions for aspen wood chip samples at 6:1liquor-to-wood ratio. Acid Sample % on Time Temperature Ethanol PL # pHwood min ° C. % wt. %* 1 2.03 1.60 104 197 68 61.4 2 1.96 2.50 42 176 5168.7 3 2.29 0.50 115 201 73 60.1 4 2.34 0.70 44 174 68 51.3 5 2.10 1.1021 166 46 38.5 *PL—precipitated lignin yield expressed as a percent ofnative lignin in wood

TABLE 2 Pulping conditions for acacia wood chip samples at 6:1liquor-to-wood ratio. Acid Sample % on Time Temperature Ethanol PL # pHwood min ° C. % wt. % 1 2.01 1.61 104 197 68 67.9 2 2.00 1.51 67 194 5866.2 3 1.96 1.40 33 181 44 51.1 4 2.35 0.60 50 205 45 51.2

TABLE 3 Pulping conditions for eucalyptus wood chip samples at 6:1liquor-to-wood ratio. Acid Sample % on Time Temperature Ethanol PL # pHwood min ° C. % wt. % 1 1.88 1.61 104 197 68 81.7 2 2.10 0.90 83 189 6469.4 3 1.77 2.41 30 170 59 61.6 4 2.30 0.61 87 183 54 65.6

For each wood chips sample, the ethanol pulping solvent was prepared tothe specified concentration by first, partially diluting the ethanolwith water after which, a suitable amount of sulphuric acid was added toachieve the target final acidity. Finally, the ethanol solution wasfurther diluted with water to achieve the target ethanol concentration.

The original lignin content of each fibrous biomass subsample wasdetermined using the methods described in National Renewable EnergyLaboratory (NREL) Technical Report entitled “Determination of StructuralCarbohydrates and Lignin in Biomass”—Laboratory Analytical Procedure(TP-510-42618 (25 Apr. 2008)). Then, after adding the fibrous biomasssample to a pressure vessel (2 L or 7 L Parr reactor (Parr InstrumentCompany, Moline, Ill., USA)) (100-700 g odw chips), the pH-adjustedethanol-based pulping solvent was added to the vessel at a 6:1liquor:wood ratio & the pH recorded. The vessel was then pressurized andbrought up to the target temperature listed in Tables 1-3 (aspen,acacia, eucalyptus, respectively). The biomass sample was then “cooked”for the specified period of time, after which, the pulping process wasstopped. After pulping, the contents of the pressure vessel weretransferred to a hydraulic 20 ton manual shop press (Airco, China). Theliquor was separated from the solids by first squeezing the pulpedmaterials in the press to express the liquor. The expressed liquor wasthen filtered through a coarse silk screen to separate expressed chipresidues from liquor stream. Next, fine particles were separated outfrom the liquor stream by filtration through fine filter paper (WhatmanN° 1). The recovered fine particles represent lignin derivatives thatwere extracted and self-precipitated out from the liquor during coolingof the pulped biomass. The particulate lignin is herein referred to asself-precipitated lignin derivatives (i.e., “SPL”). The solubilizedlignin derivatives still remaining in the filtered liquor wereprecipitated from by dilution with cold water. The lignin derivativesprecipitated by dilution with cold water are referred to as precipitatedlignin or “PL”. After determination of the dry weights of SPL and PLlignin derivatives, the relative yield of each lignin derivative wasdetermined in reference to total native lignin (sum of theacid-insoluble lignin and acid-soluble lignin) value determined for theoriginal biomass sample before pulping. The yield of PL ligninderivatives for each sample is shown in Tables 1-3 on a weight % basisrelative to their original lignin (acid-insoluble lignin plusacid-soluble lignin values).

Characterization of the Aliphatic Hydroxyl Content of Lignin DerivativesRecovered from Three Hardwood Species.

Functionalized lignin derivatives recovered from hardwood biomasssamples as described above, were analyzed to determine the content ofprimary hydroxyl groups mmol/g sample (OH-pr mmol/g) and content ofsecondary hydroxyl groups mmol/g sample (OH-sec mmol/g). These valueswere then used to calculate mmol aliphatic hydroxyl groups/g sample(OH-al mmol/g).

The hydroxyl contents were determined by quantitative ¹³C NMRspectroscopy on a Bruker 600 MHz spectrometer equipped with a cryoprobeat 300 K using ca 30% solutions of sample in DMSO-d₆. Chemical shiftswere referenced to TMS (0.0 ppm). To ensure more accurate baseline,especially in the carbonyl region (215-185 ppm), the spectra wererecorded in the interval 240-(−40) ppm. The following conditions wereprovided for the quantitative ¹³C-NMR:

-   -   1. Inverse gate detection;    -   2. a 90° pulse;    -   3. Complete relaxation of all nuclei was achieved by addition of        chromium (III) acetylacetonate (0.01 M) and using a 1.2 s        acquisition time and 1.7 s relaxation delay acquisition        parameters.

The NMR spectra were Fourier-transformed, phased, calibrated using TMSsignals as a reference (0 ppm), and the baseline was corrected by usinga polynomial function. The correction of baseline was done using thefollowing interval references to be adjusted to zero: (220-215ppm)-(185-182 ppm)-(97-92 ppm)-(5-(−20) ppm). No other regions wereforced to 0. The signals in the quantitative ¹³C NMR spectra wereassigned on the basis of 2D HSQC spectra (FIG. 1) and a known database.The spectra were integrated then using the area of the internal standard(IS), trioxane, as the reference. Each spectrum was processed (asdescribed) at least twice to ensure good reproducibility of thequantification. Some carboxyl and ester groups resonate in the resonanceregion of hydroxyl groups (171.5-166.5 ppm) in the spectra of acetylatedlignins. The amounts of carboxyl and ester groups resonated in theinterval of 171.5-166.5 ppm were determined from the spectra ofnon-acetylated lignins. The corrected content of hydroxyl groups wasobtained then by deduction of the amounts of the carboxyl and estergroups from the corresponding resonances of hydroxyl groups (Table 4).The calculation of the quantity of the specific moieties was done asfollows:

For non-acetylated lignins: X (mmol/g lignin)=I _(X) *m _(IS)/(30m_(Lig) *I _(IS))*1000

For acetylated lignins: X (mmol/g lignin)=I _(X) *m _(IS)/(30m _(Lig) *I_(IS)−42*I _(OHtotal) *m _(IS))*1000

Where X was the amount of the specific moiety; I_(x), I_(IS) andI_(OHtotal) were the resonance values of the specific moiety (Table 4),the internal standard and total OH groups, correspondingly; m_(Lig) andm_(IS) are the masses of the lignin and internal standard.

FIG. 1 shows the HSQC spectrum of non-acetylated hardwood ligninderivatives (arrows indicate the signals corresponding to the ethoxylgroups).

The recorded ¹³C NMR spectroscopic data are processed and graphicallyillustrated as shown in FIGS. 2 and 3.

TABLE 4 Symbol I_(X) in Calculation Equation Analytical Method OH-prResonance at 171.5-169.7 ppm in the Quantitative ¹³C High Resolution NMRof mmol/g quantitative ¹³C NMR spectra of lignin using 1,3,5-trioxane asinternal acetylated lignins minus resonance at reference 171.5-169.7 ppmin the quantitative ¹³C NMR spectra of non-acetylated lignins OH-secResonance at 169.7-169.2 ppm in the Quantitative ¹³C High Resolution NMRof mmol/g quantitative ¹³C NMR spectra of lignin using 1,3,5-trioxane asinternal acetylated lignins minus resonance at reference 169.7-169.2 ppmin the quantitative ¹³C NMR spectra of non-acetylated lignins OH-Resonance at 171.5-165.0 ppm in the Quantitative ¹³C High Resolution NMRof total quantitative ¹³C NMR spectra of lignin using 1,3,5-trioxane asinternal mmol/g acetylated lignins minus resonance at reference171.5-166.5 ppm in the quantitative ¹³C NMR spectra of non-acetylatedlignins OH-al OH-al = OH-pr + OH-sec mmol/g OEt Resonance at 16.0-14.5ppm in the Quantitative ¹³C High Resolution NMR of mmol/g quantitative¹³C NMR spectra (both lignin using 1,3,5-trioxane as internal inacetylated and non-acetylated reference combined with 2D HSQC lignins,calculated as average)

The aliphatic hydroxyl contents of the PL lignin derivatives from eachof the five samples of aspen chips are shown in Table 5. The contentsranged from 0.58 mmol/g in sample 1 to 2.21 mmol/g in sample 5.

TABLE 5 Aliphatic hydroxyl content and normalized radical scavengingindex of PL lignins recovered from aspen wood chips. OH-pr OH-sec OH_alRun # mmol/g mmol/g mmol/g NRSI 1 0.58 0.00 0.58 94.13 2 0.87 0.11 0.9889.64 3 1.00 0.38 1.38 67.67 4 1.24 0.54 1.78 56.62 5 1.44 0.78 2.2161.98

The aliphatic hydroxyl contents of the PL lignin derivatives from eachof the four samples of acacia chips are shown in Table 6. The contentsranged from 0.76 mmol/g in sample 1 to 2.31 mmol/g in sample 4.

TABLE 6 Aliphatic hydroxyl content and normalized radical scavengingindex of PL lignins recovered from acacia wood chips. OH-pr OH-sec OH_alRun # mmol/g mmol/g mmol/g NRSI 1 0.76 0.00 0.76 121.76 2 1.08 0.38 1.4694.91 3 1.32 0.75 2.07 75.57 4 1.48 0.83 2.31 80.44

The aliphatic hydroxyl contents of the PL lignin derivatives from eachof the four samples of eucalyptus chips are shown in Table 7. Thecontents ranged from 0.76 mmol/g in sample 1 to 2.31 mmol/g in sample 4.

TABLE 7 Aliphatic hydroxyl content and normalized radical scavengingindex of PL lignins recovered from E. nitens wood chips. OH-pr OH-secOH_al Run # mmol/g mmol/g mmol/g NRSI 1 0.57 0.13 0.70 109.65 2 0.760.69 1.46 91.16 3 1.11 0.72 1.83 77.43 4 1.20 1.07 2.27 75.58Characterization of the NRSI of Lignin Derivatives Recovered from ThreeHardwood Species.

The lignin derivatives samples produced above were assessed for theirnormalized radical scavenging index (NRSI). The potential antioxidantactivity of each PL lignin derivative was determined by measuring itsradical savaging capacity. The assay used 2,2-diphenyl-1-picrylhydrazyl(DPPH), a stabile free radical which absorbs light strongly at 515 nm tomeasure a compound's radical scavenging index (RSI). In its radicalform, DPPH═ absorbs strongly at 515 nm and has a deep purple colour. AsDPPH gives up its free electron to radical scavengers, it loses itspurple colour and its absorbance shifts to 520 nm. The greater the dropin DPPH absorbance at 515 nm after a test compound has been added to theDPPH solution, the higher the compound's free RSI and also, itsantioxidant activity. In the present study, Vit. E and BHT were used aspositive controls. PL lignin derivative subsamples (1.0-2.0 mg), Vit. Econtrol samples (1.0-2.0 mg), and BHT control samples (6.0-8.0 mg) wereprepared for testing by being placed into epitubes after which, each wasdiluted with 1.0 mL of 90% (v/v) aqueous dioxan, vortexed, transferredto new epitubes and then further diluted 50/50 with 90% aqueous dioxaneto give stock concentrations of 0.5-1.0 mg/mL for samples and Vitamin Eand 3.0-4.0 mg/mL for BHT. An indicating (purple) DPPH stable freeradical solution is made by dissolving 3.78 mg DPPH in 100 mL 90%dioxane (95.9 μM). Samples and standards are serial diluted to fillcolumns of a quartz 96-well plate (8 dilutions). The assays wereperformed by placing aliquots of the sample stock solutions into tworows of wells in a 96-well plate. The first row served as the referencerow while the second row received DPPH aliquots. 165 μL of 90% dioxanewas added to each well and mixed. Aliquots of the mixed samples in eachrow were transferred to the adjacent row and further diluted with 165 μLof 90% dioxane in each well. The mixing, transferring and dilution wererepeated until the last row of wells is prepared. The same volume ofaliquots was removed from the last row. The 96-well plate also containeda row of wells that received only the 90% dioxane. In the final step ofthe preparation procedure, 165 μL of the DPPH solution was added to allthe control and analytical columns by using an 8-channel auto-pipetteand an Eppendorf® reagent reservoir as quickly as possible. As soon asall reagents are added, the plate is placed into a plate-readingspectrophotometer (Molecular Devices, Sunnyvale, Calif., USA, SpectraMax Plus), and absorbance measurements are commenced. The program forthe spectrophotometer (SOFTmax software) consisted of a timing sequenceof 16 min and a reading of the entire plate at 515 nm. RSI (radicalscavenging index) is defined as the inverse of the concentration whichthat produced 50% inhibition in DPPH absorbance at 515 nm. The resultswere then ‘normalized’ (NRSI) by dividing the sample RSI by the RSIvalue for the BHT control.

The NRSI values for lignin derivatives recovered from aspen wood chipsare shown in Table 5. The NRSI values for lignin derivatives recoveredfrom acacia wood chips are shown in Table 6. The NRSI values for ligninderivatives recovered from eucalyptus wood chips are shown in Table 7.

Example 2 Recovery of Lignin Derivatives from Softwood Feedstocks

Softwood feedstock chips were prepared from: (1) hybrid spruce treesgrown in British Columbia, (2) radiata pine grown in Chile, and (3)loblolly pine grown in south eastern USA. Three samples of the hybridspruce wood chips were individually pulped using an acid-catalyzedethanol pulping process wherein a different set of pulping conditionswas used for each sample (Table 8). Process conditions for pulping threesamples of the radiata pine chips are shown in Table 9. Processconditions for pulping three samples of the loblolly pine chips areshown in Table 10.

TABLE 8 Pulping conditions for hybrid spruce wood chip samples at 6:1liquor-to-wood ratio. Run Acid Time Temperature Ethanol PL # pH % min °C. % % 1 2.02 1.20 58 191 46 44.84 2 2.08 1.40 43 189 61 67.77 3 2.091.60 50 183 77 72.10

TABLE 9 Pulping conditions for radiata pine wood chip samples at 6:1liquor-to-wood ratio. Run Acid Time Temperature Ethanol PL # pH % min °C. % % 1 2.04 1.20 58 191 46 34.21 2 2.12 1.40 43 189 61 65.40 3 1.921.80 46 187 49 42.72

TABLE 10 Pulping conditions for loblolly pine wood chip samples at 6:1liquor-to-wood ratio. Run Acid Time Temperature Ethanol PL # pH % min °C. % % 1 2.05 1.20 33 192 82 65.1 2 2.01 1.40 43 189 61 63.3 3 1.80 1.8046 187 49 42.3

For each wood chips sample, the ethanol pulping solvent was prepared tothe specified concentration by first, partially diluting the ethanolwith water after which, a suitable amount of sulphuric acid was added toachieve the target final acidity. Finally, the ethanol solution wasfurther diluted with water to achieve the target ethanol concentration.

The lignin content of each original fibrous biomass subsample wasdetermined using the NREL method (NREL/TP-510-42618 (April 2008)). Then,after adding the fibrous biomass sample to a pressure vessel (2 L or 7 LParr reactor (Parr Instrument Company, Moline, Ill., USA) (100-700 g odwchips), the pH-adjusted ethanol-based pulping solvent was added to thevessel at a 6:1 liquor:wood ratio & the pH recorded. The vessel was thenpressurized and brought up to the target temperature listed in Tables8-10 (spruce, radiata pine, loblolly pine, respectively). The biomasssample was then “cooked” for the specified period of time, after which,the pulping process was stopped. After pulping, the contents of pressurevessel were transferred to a hydraulic 20 ton manual shop press (Airco,China). The liquor was separated from the solids by first squeezing thepulped materials in the press to express the liquor. The expressedliquor was then filtered through a coarse silk screen to separateexpressed chip residues from liquor stream. Next, fine particles wereseparated out from the liquor stream by filtration through fine filterpaper (Whatman N° 1). The recovered fine particles represent ligninderivatives that were extracted and self-precipitated out from theliquor during cooling of the pulped biomass. The particulate lignin isherein referred to as self-precipitated lignin derivatives (i.e.,“SPL”). The solubilized lignin derivatives still remaining in thefiltered liquor were precipitated from by dilution with cold water. Thelignin derivatives precipitated by dilution with cold water are referredto as precipitated lignin or “PL”. After determination of the dryweights of SPL and PL lignin derivatives, the relative yield of eachlignin derivative was determined in reference to the total lignincontent (acid-insoluble plus the acid-soluble lignin) determined for theoriginal biomass sample before pulping. The yield of PL ligninderivatives for each sample is shown in Tables 8-10 on a weight % basisrelative to total lignin in the original biomass.

Characterization of the Aliphatic Hydroxyl Content

Functionalized lignin derivatives recovered from hardwood biomasssamples as described above, were analyzed using the procedures describedin Example 1 to determine the weights of primary hydroxyl groups mmol/gsample (OH-pr mmol/g) and weights of secondary hydroxyl groups mmol /gsample (OH-sec mmol/g). These values were then used to calculate thetotal mmol aliphatic hydroxyl groups/g sample (OH-al mmol/g).

The aliphatic contents of the PL lignin derivatives from each of thethree samples of hybrid spruce chips are shown in Table 11. The contentsranged from 1.72 mmol/g in sample 1 to 2.24 mmol/g in sample 3. Thealiphatic contents of the PL lignin derivatives from each of the threesamples of radiata pine chips are shown in Table 12. The contents rangedfrom 2.18 mmol/g in sample 1 to 2.26 mmol/g in sample 3. The aliphaticcontents of the PL lignin derivatives from each of the three samples ofloblolly pine chips are shown in Table 13. The contents ranged from 1.35mmol/g in sample 1 to 1.87 mmol/g in sample 3.

TABLE 11 Aliphatic hydroxyl content and normalized radical scavengingindex of PL lignins recovered from hybrid spruce wood chips. OH-prOH-sec OH-al Run # mmol/g mmol/g mmol/g NRSI 1 1.57 0.14 1.72 61.60 21.67 0.29 1.96 46.82 3 1.74 0.28 2.02 40.66

TABLE 12 Aliphatic hydroxyl content and normalized radical scavengingindex of PL lignins recovered from radiata pine wood chips. OH-pr OH-secOH-al Run # mmol/g mmol/g mmol/g NRSI 1 1.74 0.44 2.18 64.24 2 1.79 0.432.22 35.28 3 1.90 0.35 2.26 37.44

TABLE 13 Aliphatic hydroxyl content and normalized radical scavengingindex of PL lignins recovered from loblolly pine wood chips. OH-prOH-sec OH-al Run # mmol/g mmol/g mmol/g NRSI 1 1.16 0.19 1.35 48.73 21.55 0.03 1.58 46.95 3 1.74 0.13 1.87 53.44

Characterization of the NRSI of Lignin Derivatives

Each of the lignin derivatives samples produced above were assessed fortheir normalized radical scavenging index (NRSI) as described inExample 1. The NRSI values for lignin derivatives recovered from hybridspruce wood chips are shown in Table 11. The NRSI values for ligninderivatives recovered from radiata pine wood chips are shown in Table12. The NRSI values for lignin derivatives recovered from loblolly pinewood chips are shown in Table 13.

Example 3 Recovery of Lignin Derivatives from Annual Fibre Feedstocks

Two sets of annual fibre feedstock materials were prepared from: (1)bagasse produced from sugarcane grown and processed in Brazil, and (2)corn cobs produced in Europe. Four samples of the sugarcane bagasse wereindividually pulped using an acid-catalyzed ethanol pulping processbased wherein a different set of pulping conditions was used for eachsample (Table 14). Process conditions for pulping four samples ofshredded corn cob material are shown in Table 15.

TABLE 14 Pulping conditions for sugarcane bagasse samples at 6:1liquor-to-wood ratio. Acid Time Temperature Ethanol PL Run pH % min ° C.% % 1 2.19 2.50 61 178 66 49.76 2 2.01 3.00 23 170 66 39.56 3 2.44 1.0050 192 43 37.36 4 2.19 2.00 54 164 58 44.95

TABLE 15 Pulping conditions for corn cob samples at 6:1 liquor-to-woodratio. Acid Time Temperature Ethanol PL Run pH % min ° C. % % 1 2.182.20 100 190 67 56.58 2 2.10 2.10 67 189 51 52.01 3 2.04 2.90 32 187 6945.27 4 2.17 1.20 99 183 54 50.71

For each biomass sample, the ethanol pulping solvent was prepared to thespecified concentration by first, partially diluting the ethanol withwater after which, a suitable amount of sulphuric acid was added toachieve the target final acidity. Finally, the ethanol solution wasfurther diluted with water to achieve the target ethanol concentration.

The original lignin content of each fibrous biomass subsample wasdetermined using the NREL method (NREL/TP-510-42618 (April 2008)). Then,after adding the fibrous biomass sample to a pressure vessel (2 L or 7 LParr reactor (Parr Instrument Company, Moline, Ill., USA) (100-700 g odwchips), the pH-adjusted ethanol-based pulping solvent was added to thevessel at a 6:1 liquor:biomass ratio & the pH recorded. The vessel wasthen pressurized and brought up to the target temperature listed inTables 14-15 (bagasse, corncobs, respectively). The biomass sample wasthen “cooked” for the specified period of time, after which, the pulpingprocess was stopped. After pulping, the contents of pressure vessel weretransferred to a hydraulic 20 ton manual shop press (Aicro, China). Theliquor was separated from the solids by first squeezing the pulpedmaterials in the press to express the liquor. The expressed liquor wasthen filtered through a coarse silk screen to separate expressed chipresidues from liquor stream. Next, fine particles were separated outfrom the liquor stream by filtration through fine filter paper (WhatmanN° 1). The recovered fine particles represent lignin derivatives thatwere extracted and self-precipitated out from the liquor during coolingof the pulped biomass. The particulate lignin is herein referred to asself-precipitated lignin derivatives (i.e., “SPL”). The solubilizedlignin derivatives still remaining in the filtered liquor wereprecipitated from by dilution with cold water. The lignin derivativesprecipitated by dilution with cold water are referred to as precipitatedlignin or “PL”. After determination of the dry weights of SPL and PLlignin derivatives, the relative yield of each lignin derivative wasdetermined in reference to the total lignin (sum of acid-insolublelignin plus acid-soluble lignin) value determined for the originalbiomass sample before pulping. The yield of PL lignin derivatives foreach sample is shown in Tables 14-15 on a weight % basis relative totheir original total lignin values.

Characterization of the Aliphatic Hydroxyl Content

Functionalized lignin derivatives recovered from annual fibre biomasssamples as described above, were analyzed using the procedures describedin Example 1 to determine the primary hydroxyl groups mmol/g per sample(OH-pr mmol/g) and the secondary hydroxyl groups mmol/g sample (OH-secmmol/g). These values were then used to calculate total mmol aliphatichydroxyl groups/g sample (OH-al mmol/g).

The aliphatic content of the PL lignin derivatives from each of the foursamples of sugarcane bagasse biomass are shown in Table 16. The contentranged from 1.74 mmol/g in sample 1 to 2.34 mmol/g in sample 4. Thealiphatic content of the PL lignin derivatives from each of the threesamples of shredded corn cobs are shown in Table 17. The content rangedfrom 2.18 mmol/g in sample 1 to 2.26 mmol/g in sample 4.

Characterization of the NRSI of Lignin Derivatives

Each of the lignin derivatives samples produced above were assessed fortheir normalized radical scavenging index (NRSI) as described inExample 1. The NRSI values for lignin derivatives recovered fromsugarcane bagasse biomass are shown in Table 16. The NRSI values forlignin derivatives recovered from corn cob biomass are shown in Table17.

TABLE 16 Aliphatic hydroxyl content and normalized radical scavengingindex of PL lignins recovered from sugarcane bagasse biomass. OH-prOH-sec OH-al Run mmol/g mmol/g mmol/g NRSI 1 1.02 0.73 1.74 52.34 2 1.190.89 2.09 41.80 3 1.02 1.17 2.20 46.90 4 1.31 1.02 2.34 38.74

TABLE 17 Aliphatic hydroxyl content and radical scavenging index of PLlignins recovered from corn cobs biomass. OH-pr OH-sec OH-al Run mmol/gmmol/g mmol/g NRSI 1 0.95 0.63 1.58 45.15 2 0.64 1.22 1.86 45.99 3 0.741.42 2.16 38.37 4 1.24 1.11 2.35 48.99

1. A lignin derivative wherein said lignin derivative has an aliphatichydroxyl content of 2.35 mmol/g or less.
 2. A lignin derivativeaccording to claim 1 wherein the derivative has an aliphatic hydroxylcontent of about 2.25 mmol/g or less.
 3. A lignin derivative accordingto claim 1 wherein the derivative has an aliphatic hydroxyl content ofabout 1.75 mmol/g or less.
 4. A lignin derivative according to claim 1wherein the derivative has an aliphatic hydroxyl content of about 0.1mmol/g or greater.
 5. A lignin derivative according to claim 1 whereinthe lignin is derived from hardwood biomass.
 6. A lignin derivativeaccording to claim 1 wherein the lignin is derived from softwoodbiomass.
 7. A lignin derivative according to claim 1 wherein the ligninis derived from annual fibre biomass.
 8. A lignin derivative accordingto claim 1 wherein the lignin is derived from biomass comprising Populusspp, Eucalyptus spp., Acacia spp., or combinations/hybrids thereof.
 9. Alignin derivative according to claim 1 wherein the biomass comprisesPopulus tremuloides, Eucalyptus globulus, Acacia dealbata, orcombinations/hybrids thereof.
 10. A lignin derivative according to claim1 wherein the lignin is derived from biomass comprising pine; spruce; orcombinations/hybrids thereof
 11. A lignin derivative according to claim1 wherein the lignin is derived from biomass comprising Pinus radiata,Pinus taeda, BC spruce, or combinations/hybrids thereof.
 12. A ligninderivative according to claim 1 wherein the lignin is derived frombiomass comprising wheat straw, bagasse, corn cobs, orcombinations/hybrids thereof.
 13. An annual fibre lignin derivativewherein said lignin derivative has an aliphatic hydroxyl content of 3.75mmol/g or less.
 14. A lignin derivative according to claim 1 having anormalized RSI of 15 or greater.
 15. A lignin derivative according toclaim 1 wherein the derivative comprises alkoxy groups.
 16. Use of alignin derivative according to claim 1 as an antioxidant.
 17. Use of alignin derivative according to claim 1 as an antioxidant forthermoplastics.
 18. Use of a lignin derivative according to claim 1 in afor a nutritional supplement, nutraceutical, animal feed, and/orfunctional food.
 19. A composition comprising a lignin derivativeaccording to claim 1 and a polymer-forming component.
 20. Athermoplastic composition comprising a lignin derivative according toclaim
 1. 21. A polyolefin composition comprising a lignin derivativeaccording to claim
 1. 22. A method of producing a lignin derivativeaccording to claim 1, said method comprising: a) pulping a fibrousbiomass in a vessel with an organic solvent/water solvent solution toform a liquor, wherein: i. the solution comprises about 30% or greater,by weight, of organic solvent; and ii. the pH of the liquor is fromabout 1 to about 6; b) heating the liquor to about 100° C. or greater;c) maintaining the elevated temperature and pressure for 1 minute orlonger; d) separating the cellulosic pulps from the pulping liquor; ande) recovering derivatives of native lignin.